Process of and means for forming nitrogenous compounds



. stances as UNITED STATES I PATENT OFFICE.

JOHN COLLINS CLANCY, OF FBEEPORT. NEW YORK, ASSIGNOR TO THE NITROGEN COK- PORA'LION, OF PROVIDENCE, RHODE ISLAND. A CORPORATION OF RHODE ISLAND.

PROCESS OF AND MEANS FOR F0 ammo mrnoomvous oomroonns.

Patented Sept. 7, 1920.

I 1,352,176; Specification of Letters Patent. Ho Drawing. Application filed September 1, 1917. Serial To all whom it may concern:

Be it known that l,JonN (.oLLms CLANGY, a citizen of the United States, residin at Freeport, in the county of Nassau an tate of New York, have invented certain new and lytically and in substantially a single 0poration.

()ne of the principal objects of the novel process herein described is, therefore, to cheapcn the cost of production of such subthosc aforesaid, while another and subsidiary object, which bears more especially upon the cost of upkeep of the apparatus involved in the ctfcctuation of the nitrogen fixation, is to provide a process which permits of the fixation or corresponding operation being carried out at a reasonablylow temperature; the upper limit of temperature being preferably not in excess of a moderate red heat.

Another, object of my vide a new and particularly efiieient catalyzer and in one aspect of said invention, the steps involved in the production of said catalyzer may be regarded as steps of the process as a whole.

These 31nd other objects will, hence, be hereinafter more especially referred to and the features of importance and novel combinations of steps and elements will be more particularly set forth in the claims appended hereto.

Considering first the mode of forming and nature of the catal aer or catalyzers, preferred for use in t to step or operation of fixing nitrogen in acordance with my proccss,-I have discovered that several features are of rent importance in connection therewith. irst, it IS extremely desirable that the catalyzer should be of a particu larly porous nature. such as that hereinafter referred to,in order that the gases which invention is to propass therethrough during the nitrogen fixation operation, may freely penetrate and pass out of said catalyzcr while at the same time the gaseous stream or streams are sothoroughlydivided by their passage through minute conduits in said catalyzer, that substantially all of the molecules thereof must make contact with the walls of said conduits.

I have also discovered that the catalyzer should preferably consist of or comprise a labile substance or compound such as is already carbo-nitrogenous, or which can readily. form such a carho-nitrogenous compouiu or compounds; and, in gencrahsuch preferably porous calalyzers may be formed not alone from carho-nitrogenons substances, but also from nilrids, alnids, or hybrids, if, for.e.\':unple, such hybridshavc been derived, or are capable of being derived, primarily from ca rbo-nitrogenous catalyzers prepared as hereinafter described.

Hcrctofore. to the best of my knowledge, cyanamids of various metals, such as barium cyanamid. have been formed from their cyanids by the abstraction of carbon therefrom, but. I have discovered that such cyanids may be treated with nitrogen, in a novel manner; to convert them to their cyanamids and that the soformed cyauamid of barium, for example. possesses rather extraordinary characteristics: one of the most striking features about itbcing the expanded, very porous form of the resulting material.

Thus \vhcn,for example.cyainid of barium is slowly heated up to about 400 to 500 in an atmosphere of nitrogen a reaction occurs which. I am of the opinion, may be expressed as follows:

latter is greatly ex-- of these minute pores in a given lump or mass interconnect with the result that gases may be assed therethrough with great freedom.

n the foregoing I have-assumed that this expanded c anogen compound is a simple cy'anamid; ut as to this I cannot be absolutely oeitain, it being possible that some more complex cyanogen compound than the cyanamid is the actual product. Be that as it may, however, the substance is exceedingly porous and active catalytically when used as hereinafter described; while it far thermore is self-sustaining and hence needs no support" such as is commonly provided in various catalyzers. In other words, there is no diluent, so to speak; but the entire mass may be a catalytic one. Barium cyanamid, as I hence prefer to term it, is by no means the only substance thus capable of being used as a catalyzer; since various other metals may be substituted for barium. Thus nickel eyanid may be treated with nitrogen at about 400 to 500 (7., with production of a catalytically active product.

In like or similar fashion, the catalyst may comprise tungsten, vanadium, uranium, manganese, chromium, titanium, etc; said catalystin each such case being preferably a cyanamid of the particular metal or metals selected; although in some cases even the metal itself is available for use as .a catalvst.

It should be observed, however, that with the exception of the cyanamid of barium the remaining above specifically mentioned, metal cyanamids do not thus so markedly expand during formation; and since I have discovered, further, that a mixture of catalyzers affords even more excellent results, i prefer to mix barium cyanid with the ut nids of, for example, uranium and rhro' mium, so that after treatment with nitrogen as above indicated, the whole mass is properly expanded, porous and, preferably, self sustaining.

B this expression self-sustaining, as used herein, I mean, of course, laterally selfsupporting, in that a given lump or mass of this substance possesses sufficient coherence to maintain its shape, in contra-distinction to pulverulent substances which are not thus laterally self-supporting.

Care must be exercised in preparing the expanded mass and the cyanid or cynnids from which it is prepared should be heated very gently since otherwise the desired formation will not result. Thus barium cyanid fuses at about (350 C, and it is undesirable to heat it even quite to its fusing point.

After the catalytic product has been obtained, it is cooled in an atmosphere of nitrogen to avoid oxidation thereof and is then ready for use. In appearance it is usually somewhat spongy, although.substantiully non-resilient, and in color is almost invariably black. When in use as a catalyzer, as hereinafter described, care must be taken to avoid fusing or sintering it, although after having once been formed it may be more highly heated,-usually and depending upon the substances of which it is made up,-than when efl'ectin its formation. I prefer, however, to he (1 the higher limit of temperature, at which it is used to fix nitrogen in the form of hydroeyanie acid. to about 900 (7.; although in some cases this temperature may be exceeded,-depemling on the eatalyzer employed.

llydrocyanie acid may, however, still be formed in appreciable Quantities at a much lower temperature, a. y about 400 (3.; but preferably the operation now'to be described is conducted at a red heat.

'lhus,when at about. for example. the temperature specified, mixed hydrogen, nitrogen and a suitable (tlllmlillUQOllS gas are passed through the pores of the entalyzer, hydrocyanic acid gas will be formed; the following equations being typical:

H, N ZCH, catalyzer A+ 2 IICN 4H, catnlyzer;

II N, QII, -l catalyzer A) 2IICN II, catalyzcr.

Preferably the hydrocarbons are thus employed as sources of carbon (and also at times as sources of hydrogen) but if barium cyanamid be absent from the catalyzer, carbon monoxid may be as readily used, especially if the catalytic agent or agents be properly distended or supported. Indeed, oven ii this barium compound be present it is still possible to use rarbon lnonoxid; but at some sacrifice in ellicicnry of the catalyzcr. \Vhat happens in this case is that the barium cyanamid is oxidized to barium oxid (IMO); probably taking its oxygen-from the water formed or from the carbon ,inonoxid direct. As a catalyst the ellicicncy of this substance is hence impaired if not destroyed. ()n the other hand, it has performed a part of its function, having expanded the catalytic mass as a whole, so that the remaining catalytic materials are free to art.

The following equation probably repre sents what takes plure when barium oxid is thus lornn-xl;

IlaCN, CO-dlaO C,N,.

If carbon iuonoxid, for example, is used,

' how: rer, there is the advantage thatjt does the fact that heretofore the synthesis of such q mpounds has, I believe, always been ctfecte'uat from 1800 C. to 2500 C. so that the value of the catalytic process herein described,which permits the desired reaction to occur at temperatures considerably below even 1200 ,(l, (or in other words at from onethird to one-half the temperatures formerly employed, e. g., 600--9(K) (.),becomes at once apparent, from a consideration of this fact alone.

' \Vhile the synthesis of hydrocyanic acid may thus be broughtabout at pressures approximating that of the atmosphere; I preferto operate under pressure; since the cfiicicncy of the reaction is thereby materially increased. In fact, this increase in pressure operates in two beneficial ways. In the first place, the molecules of nitrogen, hydrogen and the gaseous hydro-carbon or other source of carbon, are driven more intimately together and, when passing through the pores of the catalyzcr, correspondingly more efficiently in contact with the walls of said pores, whereby a more copious yield results. lnthe second place, since the higher the temperature the more eflicient the reaction it is desirable to operate at a fair red heat and the increase in pressure tnon the material of the catalyzer permits of appreciable elevation of the temperature while still maintaining the latter within the limit of safety to the catalyzer; since the pressure upon the latter raises its fusion or sintcrin point.

Ihence prefer to operate at pressures ran ging from pounds per square inch up to 1000 pounds per square inch, or more, de pending upon the limit of cost of the apparatus. By this is meant that in any apparatus in which gas under pressure is heated or into which gases at high temperature and under high pressures are introduced, there is a mechanical limit which is imposed by the nature of the apparatus cmployed,-and necessarily for a given temperature, as the pressure used becomes increasingly greater, beyond certain obvious limits, the cost of the apparatus becomes more than correspondingly greater.

The hydrocyanic acid so produccd,-if in gaseous form, as will normally be the case when operating at a redheat,-may be separated from the gaseous reaction residues or unchanged gases in any suitable manner, as by means of caustic soda or by forming liquid hydrocyanic acid, or a derivative thereof.

As illustrative of the powerful catalytic properties of my improved catalytic matcrial,.-whether comprising but one of the indicated substances or as is to be preferred, the peculiarly intimate mixture of a plurality of the same, prepared substantially as, aforesaid, or derived from the expanded cyanogen complex mass,I may point out that if no hydrogen be present in the mixture of" nitrogen and carbon supplying gas, supplied to the catalyzer at reaction temperature, hydrocyanic acid will not be formed; but in lieu thereof cyanogen gas will pass off from said catalyzer. lVhen, however, hydrogen is supplied, especially in molecular condition, hydrocyanic acid 'may be formed as above described.

Aside from the chemical constitution of one or more of these elements of the novel catalytic material, I attribute much of the high catalytic power of the preferred catalyzer or catalytic mixture to its peculiar structure which offers to the gases to be synthesized or combined, contact surfaces of extraordinary extent and especially adapted to ramify, so to speak, the gaseous stream, so as to enable the moleculcs of the elements to be combined, to more readily make contact. therewith.

On the other hand where, for various purposes, catalytic material has been used in pulvcrulent fo rm, if the mass to be penetrated by the gas is of any material depth, it tends to obstruct the flow of said gas, while if the latter be forced through the powder, it of course tends to displace the lattcr from its support.

\Vhilc as per the foregoing, I have dcscribcd a class of catalytic materials which are capable of formation into a substantially self-supporting structure, which in most cases is to be prefcrred,-I do not wish to have my invcntion, in its broader aspects regarded as being limitcd to these or to their use in the proccss as a whole; since I am aware of various other agents which are capable of being used as catalyy'crs for the formation of, for example, hydrocyanic acid.

Thus, by my of illustration, have discovered that the cyanid of an alkali metal, e. potassium or sodium, may be heated to about a-red heat or even somewhat lower, togethcr with hydrogen, nitrogen and carbon or a substance or substances to yield one or more of those elem nts to form a fairly good catalyzcr, which, however, should preferably be provided with a support,-in .which it, is unlike the other cyanogen-complcx catalyzcrs to which I have referred; the alkali metal catalytic compound so produccd not bcing cxpandcd. It may, however. be flowed in thin films ovc' asbestos wool, kiesclguhr, coke or the like, to provide a. catalytic body of adequate porosity; and when, for example, mixed hydrogen, nitrogen and a suitable carlmlmccous gas are passed under pressure and at about a red heat through or in contact with those films, liywlrocyanic acid gas will be synthetically produced.

The material from which the catalyzcr is to be formed may also be. for example,

an amid of a suitable metal. Thus, when hot chromic acid is treated with ammonia gas, there is formed an incandescent mass of what is apparently chromium amid, which sinters, and which, after cooling, may be broken into small particles to form a fair -atalyzer; which, however, if so used is by no means comparable with the chromium cyanogen complex catalyzer above mentioned.

A similar and very eflicient catalyzcr, however, is obtained 1y substituting tung- Sten for chromium in the catalytic compound. Thus by treating ammonium tungstate with animonia at 350 0., a black shiny crystalline mass,-- whichpresumably is tungsten amid,is formed. This is a catalyzer which when treated at about 850 C. with hydrogen and nitrogen, together with acetylene, carbon monoxid or other suitable carbon supplying gas,evcii though the gases employed are not under prcssurc. affords a large yield of hydrocyanic acid. The yield of hydrocyanic acid is, moreover, increased by rising the gases under pressure. Again, by way of exam ile, if gaseous ammonia be substituted t er nitrogen and hydrogen, a mixture of one part thereof with two parts of acetylene gas may be sub jccted to a catalyzer of tungsten metal, alone, to afford a copious yield of hydrocyanic acid at about 750 (1., especiallywhen the gases are under moderate pressure.

The catalyzer, in view of the abo'vc cx cmplifications may hence be varied greatly, both as regards its structure and initial ma terial,the metals specified being capable of forming or of being converted into the desired labile valenccd compounds,

In like manner other metals than llliii mium or tungsten are available for lll(()l -poration in the catalyzer, as, for example, titanium, vanadium, manganese, uranium, etc, which may be obtained if desired, from various salts or compounds thereof, c. r hydrids; but which on account of the novel structure of the preferred catalyzer are preferably incorporated thereinto as, or converted therein in aim to, expanded complex cyanogen compounds thereof such as those produced in manner aforesaid.

Ilowcvcr, titanium, vanadium, tungsten, uranium and chromium, for example, when prcpai'cd as their cyananiids or indeed even as cyanids, in relatively compact masses and without cxpaiisirm by the barium cyanogen complex or the likc. bchavc excellently as catalyzcrs for lrvdrocyanic acid production, cspccially whcn operating undcr higher prcssurcs, as per tlic tori-going.

In conclusion. I may add that \vliilc the production of ll \lll'lll \'illllt acid by I|Hl. i-\' |'caction is of coursihnown, so far as I am aware the usc f a true catalyst in this coniicction has new.- even been suggested; and

certainly not for use in a process of this dcsci'iptioii where the temperature of the operation is maintained around or below a red heat.

I am also aware that both my preferred catalyzers and the modes of using the same are capable of yielding other products than those specifically referred to herein, so that where, in the appended claims, I do not specifically mention carbon, for example, but refer to the element to be combined with nitrogen simply as an element," it will be lllltltflStOOtl that I do not in such case contemplate limiting inystclt to carbon. Moreover, generic claims which more particularly concern my novel catalytic material, are intended to cover said materials, no mattcr how used or modified, except as in some cases otherwise expressly stated in said claims; on account of the extreme adapt ability of said material to the formation of derivatives thereof, as hereinbeforc de scribed.

llaving thus described my invention,

what I claim is:

I, The process of producing a carbonitrogenous compound which comprises effecting a nitrogen fixing reaction by subjecting a carho-nitrogenous catalyzer to free nitrogen and to a carbonaceous gas capable of acting as the source of the carbon for the carbo-nitrogenous compound to he formed 2. The process of producing a carbonilrogenous compound which comprises snhjccting a gaseous mixture which is under sopcr-atinospheric pressure and in which are present the clcii'icnts hydrogen, nitrogen and carbon, to contact with a catalyze! capable of svnthctically uniting at least the two last mentioned elements, said pressure being in excess of thirty pounds per square inch. i

3. The process of producing a nitrogenous compound whicli con priscs subjecting a gaseous mixture which is under superatmospheric pressure and in which are present the elements hydrogen, nitrogen and 'arbon, to contact with a catalyzer, in the solid phase, which is capable of synthetically uniting said nitrogen to at least one of the remaining elements aforesaid, said pressure being in excess of 30 pounds per square inch.

4. The recess of producing a substance in which is present the radical CN, which comprises synthetically uniting the elements carbon and nitrogen, to form said radical,

by subjecting gaseous material which inchides said elements to contact with a heated catalytic mass in which is a compound containing carbon unitcd to nitrogen by a plui'alit v of bonds.

The process of fixing nitrogen which comprises synthetically uniting free nitrocomprises synthetically gen to at least one other element through the intermediacy of a catalytically active derivative of a cyanogen compound and which mass has been expanded by the gen eration of gas therein during its conversion from said cyanogen compound.

(l. The process of fixing nitrogen which uniting tree nitrogen to at least one other element through the intermediacy of a catalytically active derivative of a cyanogen compound and which mass has been expanded by the generation of gas therein.

7 The process of fixing nitrogen which comprises synthetically uniting free nitro gen to carbon and hydrogen, through the intermediacy of a catalytically active deriw ative of a cyanogen compound and which mass has been expanded by the generation of gas therein.

8. The process of producing a catalyzor for nitrogen fixation and the like, which comprises gaseously distending a mass of catalyzer-forming carbonaceous material by treating said material to effect therewith a gas evolving reaction, in which said material participates to yield a part only of its carbon content for the formation of said gas and to form a spongy substance the pores of which may readily be traversed by gases.

9. The process of producing a catalyzcr for nitrogen fixation and the. like, which comprises treating material containing carbon and nitrogen united by a plurality of bonds, to liberate cyanogen therefrom in gaseous form while said material is in the solid phase but in plastic condition, and permitting the gaseous cyanogen to expand the plastic residues during the evolution of said gas, to open a multiplicity of pores throughout said material, whereby to im part catalytic properties to said material by the separation of cyanogen therefrom while simultaneously utilizing the gaseous cyanogen during the course of its said separation, as a means for impartinga porous form to the catalytic material.

10. The process of producing a catalyzer which comprises effecting a reaction, in part at least through the intermcdiacy oi heat, within a mass of material which includes a carbo nitrogelious compound, to liberate a carbo-nitrogenous gas therefrom and form a second carho-nitrogenous compound which possesses the desired catalytic properties.

11. The process of producing a porous catalyzcr, which comprises gascously ex panding a reactive mass into a sponge-like substance by the evolution of gas in said mass while simultaneously rendering constitnents of said mass catalytically active. said substance including as an essential constituent thereof an element which is also an essential constituent of said gas.

12. The process of producing a catalyzcr which comprises mixing together a pluralit) ol carbo-nilrogcnous substances one of which is capable of being expansively reacted upon and another of which is less thus capable. said othcr h w vcr. being capable f c nver i n into an active catalyst, subjecting thc mixture to treatment, including heat, to cxpansively react upon said first mentioned substance and to produce said active catalyst in distended form, in part at least through the interniediacy of the expansive force generated and exerted in said first mentioned substance as the latter IS being cxpansively reacted upon.

13. The process of producing a catalyzer which comprises mixing together barium cyanid and another cyanid which is capable of conversion into an active catalyst, subjecting the mixture to heat. in an atmosphere of nitrogen to form an expanded barium,.cyanogen complex and to convert said other cyanid to said active catalyst in distended form. in part at least through the intermediary of the expansive force generated and exerted in said barium cyanid as the latter is being converted to said ex pandcd complex.

14. The process of producing a catalyzer which comprises mixing together a plurality of metal cyanids and reacting upon the mixture with a nitrogenous reagent to form an expanded mass of complex cyanogen compounds.

15. The process of producing a nitrogeniixing catalyzcr which comprises treating barium cyanid to ell'ect a substitution of-nitrogen for a part of the cyanogen content of said cyanid at a temperature below (3.30 t.

lti. 'lhc process oi producing a nitrogen fixing catalyzcr which comprises treating an ;tll(:lllllt tiil'lll metal cyanid to eil'cct a substitution ol' nitrogcn for a part of the cyanogcn content ol'said cyanid at a tcmpcra tillc below (350 v 1?. 'l hc process of producing a substance which compriscs converting a simple mctal cyanid to n cyanogen derivative thereof, by reacting upon said yanid to liberate carbon therefrom in combination with nitrogen at a tcmpcraturc below (350 t.

15. the proccss'uf producing a catalyst which comprises rcndcring a mass of carbo nitrogenous catalystyielding material porous by evolving a carlmnaccous gas thcrc within. in part. at least from the substance thereof.

11). The process of producing hydrocyanic acid which comprises subjecting mixed ummonia and acetylene gas to contact with a reactiowell'ccting catalyze! at a temperature approximating a red heat.

'20. l hc process of producing a catalyst which comprisesrendering a mass of. carbonitrogenous catalyst-yielding material porous by evolving a nitrogenous gas therewithin, in part at least from the substance thereof and allowing said gas to act expansivcly to open up porcs'in said material, then cooling said material to reduce the plasticity thereof and preserve said pores.

21. A gaseously expanded, catalytically active Garbo-nitrogenous substance.

22. Aratalyzcr which comprises a. deriva tive of an unfused gaseously expanded cyanogen compound, the expanded structure of which is preserved in said derivative.

23. As an article of manufacture, a spongy, self-supporting catalytically active derivative of a cyanogen compound.

24. The process of producing a carbonitrogenous compound which comprises synthetically forming said compound through the intermediacy of a catalytically active. (yanid derivative produced in an atmos phere of nitrogen.

25. The process of producing a carbonitrogenous compound which comprises effecting a reaction between substances in the gaseous state, elements of which are v capable of combining with arbon to yield said compound, through the intermediary of carbo-nitrogenous material, by bringing said substances, while intimately mixed. into contact with said material, and supplying carbon to said material to replace that removed from said material by said reaction.

26. The process of producing hydrocyanir acid which comprises synthetically and cat alytically combining hydrogen. carbon and nitrogen at a temperature above 500 t. through the intermediary of a nitrogenous substance.

27. The process of producing hydrocyanic arid which comprises uniting the elements of said acid through the intermediacy of a fusible non-metallic catalyzer at a temperature. below that at which said catalyze! fuses.

28. The process of producing hydrocyanic acid which comprises uniting the elements of said acid synthetically while in gaseous condition, through the intermediacy of a fusible catalyzcr, at a temperature below the sintering point of said catalyzcr but above one" 225 The process of producing hydrocyanic acid which comprises uniting the elements of said acid synthetically while in gaseous condition, through the intcrmediacy of a fusible catalyzer, at a temperature below the sintering point of said catalyzer, and while said elements are under pressure.

Jill. The process of producing a nitrogen Iixing catalyzcr from carbo-nitrogenous ina terial. which comprises ell ccting a reaction to reduce the carbon content of said mate rial by combining carbon thereof with ni trogen to form a gaseous carbo-nitrogenous substance St The process of producing hydrocyanic a id which comprises subjecting a gaseous mixture, one of the elements of which is hydrogcnous in character and another of which is a. hydro-carbon, to contact with a rcai-tion-eilccting catalyst heated to a tempcrature above 500 C.

In testimony whereof I have atlixed my signature, in the )resence of two witnesses.

JOHi UOLLlNS CLANCY.

\Vitnesscs:

Gun. 1. GEnrIN, FnANeis G. Smi'rn. 

